US3141770A - Electrophotographic layers and sensitizers for same - Google Patents

Electrophotographic layers and sensitizers for same Download PDF

Info

Publication number
US3141770A
US3141770A US163017A US16301761A US3141770A US 3141770 A US3141770 A US 3141770A US 163017 A US163017 A US 163017A US 16301761 A US16301761 A US 16301761A US 3141770 A US3141770 A US 3141770A
Authority
US
United States
Prior art keywords
perchlorate
bis
photoconductive
thiapyrylium
pyrylium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US163017A
Inventor
Dale R Davis
Cornelia C Natale
Charles J Fox
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DENDAT1252060D priority Critical patent/DE1252060B/de
Priority to BE626528D priority patent/BE626528A/xx
Priority to BE623972D priority patent/BE623972A/xx
Priority to US146743A priority patent/US3250615A/en
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US163017A priority patent/US3141770A/en
Priority to DE19621572340 priority patent/DE1572340B1/en
Priority to FR913039A priority patent/FR1359095A/en
Priority to GB40183/62A priority patent/GB1023377A/en
Priority to JP5285962A priority patent/JPS3911543B1/ja
Priority to DEP1269A priority patent/DE1269488B/en
Priority to FR919425A priority patent/FR86809E/en
Application granted granted Critical
Publication of US3141770A publication Critical patent/US3141770A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/0622—Heterocyclic compounds
    • G03G5/0624—Heterocyclic compounds containing one hetero ring
    • G03G5/0635—Heterocyclic compounds containing one hetero ring being six-membered
    • G03G5/0637—Heterocyclic compounds containing one hetero ring being six-membered containing one hetero atom
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/09—Sensitisors or activators, e.g. dyestuffs

Definitions

  • the present invention relates to electrophotography and to photoconductive substances for preparing photoconductive layers for use in processes of electrophotography. More particularly, the present invention relates to such layers having incorporated novel sensitizing compounds.
  • Electrophotographic processes which depend on photoconductive layers include (a) xerographic processes in which, for example, a photoconductive layer on an electrically conducting support is provided with a uniform electrostatic charge in the dark, given an image exposure to light which causes the charge to be selectively dissipated in proportion to the intensity of the incident radiation, and then toned with a powder having optical density which adheres in the areas of residual charge, and (b) photoconductographic processes in which, for example, a photoconductive layer provides in areas of image exposure sufficient conductivity to enable formation of a visible image by an electrolytic process activated by an externally applied source of electric current. Processes of these types have been described in such US. and foreign patents as US. 2,297,691; 2,551,- 582 and in British 188,030 and 464,112.
  • Photoconductive layers for use in electrophotographic processes of the present type have been prepared in the past using such photoconductors as selenium, cadmium sulfide and zinc oxide. More recently, certain organic compounds have been proposed for use as photoconductors in photoconductive layers. Organic compounds, although preferred for other reasons, such as their capacity to form transparent layers and the like, have not shown in many cases a sensitivity to light to give the speed values desired in layers of this type.
  • a number of sensitizing compounds have been disclosed recently in the prior art for use with certain of the organic-type photoconductor compounds. It is an object of the present invention to disclose still other classes of sensitizing compounds for use in combination with certain organic photoconducting compounds so that improved speed in photoconducting layers is obtained.
  • An object of the present invention accordingly, is to provide novel sensitizing compounds for use in photoconductive electrophotographic layers. Another object is to provide novel photoconductive layers having improved photoelectric speed. Other objects will become apparent from a reading of the specification and appended claims.
  • Arylamines to which we refer in the present specification comprises (1) diarylamines such as diphenylarnine, dinaphthylamine, N,N-diphenylbenzidine, N-phenyl-l-naphthylamine, N-phenyl-Z-naphthylamine, N,N-diphenyl-p-phenylenediamine, 2-carboxy-5-chloro- 4'-methoxydiphenylamine, p-anilinophenol, N,N'-di-2- naphthyl-p-phenylene diamine, and the like, and (2) triarylamines including (a) nonpolymeric triarylamines, such as triphenylamine, N,N,N,N-t
  • Pyrylium salts and thiapyrylium salts of the present invention comprise compounds represented by the following general formula:
  • R R and R may each represent an aliphatic group having from 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl, vinyl, styryl, alkoxystyryl, diethoxystyryl, dimethylaminostyryl, 1-butyl-4-pdimethylaminophenyl-1,3-butadienyl, ,B-ethyl-4-dimethylaminostyryl; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy, etc.; aryl, such as phenyl, 4-biphenyl, alkphenyl, such as 4-ethylphenyl, 4-propylphenyl, etc.
  • Typical members of the present pyrylium and thiapyrylium salts include the following: 7
  • 27 4-(4-Dimethylaminophenyl)-2,6-diphenylpyrylium perchlorate.
  • G-Ethyl-zA-diphenylpyryliumfluoborate 2,6-Bis(4-ethylphenyl)4-(4-methoxyphenyl)thlapyrylium chloride. 53 6-[fi,B-Bi's(4-dimethylaminophenyl)v1nylene]-2,4-d1(4- ethylphenybpyrylium perchlorate. v 2,6-Bis(4-amyloxyphenyl)-4-(4-methoxyphenyl)thiapyrylium perchlorate.
  • sensitizer which can be addedgtoda acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate, vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(methyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl) methacrylate), etc.; polystyrene; nitrated polystyrene; polymethylstyrene; isobutylene polymers; polyesters, such as poly(ethylene alkaryloxyalkylene terephthalate); phenol-formaldehyde resins; ketone resins; polyamide; polycarbonates; etc.
  • styrene-alkyd resins can be prepared according to the method described in US. Patents 2,361,019 and 2,258,423.
  • Suitable resins of the type contemplated for use in the photoconductive layers of this invention are sold under such trade names as Vitel PE-lOl-X, Cymac, Piccopale 100, and Saran F- 220.
  • Other types of binders which can be used in the photoconductive layers of the invention include such materials as paraflin, mineral Waxes, etc.
  • Solvents of choice for preparing coating compositions of the present invention can include a number of solvents such as benzene, toluene, acetone, Z-butanone, chlorinated hydrocarbons, e.g., methylene chloride, ethylene chloride, etc. ethers, e.g., tetrahydrofuran, or mixtures of these solvents, etc.
  • solvents such as benzene, toluene, acetone, Z-butanone, chlorinated hydrocarbons, e.g., methylene chloride, ethylene chloride, etc.
  • ethers e.g., tetrahydrofuran, or mixtures of these solvents, etc.
  • Photoconductive layers of the present invention can be coated on a conducting support in any well-known manner such as doctor-blade coating, swirling, dip-coat ing, and the like.
  • Photoconductive layers of the invention in some cases do not require a binder, for example, where certain polymeric arylamines are employed. However, it has been found beneficial sometimes to include in a coating composition of this type at least some binder, for example,. as little as 1 weight percent.
  • the photoconductor substance was present in an amount equal to at least about 1 weight percent of the coating composition.
  • the upper limit in the amount of photoconductor substance present is not critical.
  • the polymeric materials of thepresent invention in many cases do not require a binder in order to obtain a self-supporting coating on the support. In those cases Where a binder is employed, it.
  • the photoconductor substance be present in an amount from about 1 weight percent of the coating composition to about 99 weight percent of the coating composition.
  • a preferred weight range for the photoconductor substance in the coating composition is from 10 weight percent to about 60 weight percent.
  • Coating thicknesses of the photoconductive composition on a support can vary widely. Normally a wet coating in the range from about 0.001 inch to about 0.01 inch was useful for the invention. The preferred range of Wet coating thickness was found to be in the range from about 0.002 inch to about 0.006 inch.
  • Suitable supporting materials for coating the photoconductive layers of the present invention can include any of the electrically conducting supports, for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, zinc, brass, and galvanized plates; regenerated cellulose and cellulose derivatives; certain polyesters, especia1- ly polyesters having a thin electroconductive layer (e.g., cuprous iodide) coated thereon; etc.
  • ing materials can also include the humidity-independent conducting layers of semiconductors dispersed in, poly:
  • the elements of the present invention can be employed in any of the well-known electrophotographic processes which require photoconductive layers.
  • One such process is the xerographic proces.
  • the electrophotographic element is given a blanket electrostatic charge by placing the same under a corona discharge which serves to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial insulating property of the layer, i.e., the low conductivity of the layer in the dark.
  • the electrostatic charge formed on the surface of the photoconducting layer is then selectively dissipated from the surface of the layer by exposure to light through a negative by a conventional exposure operation such as, for example, by contact-printing technique, or by lens projection of an image, etc., to form a latent image in the photoconducting layer.
  • a charged pattern is created by virtue of the fact that light causes the charge to leak away in proportion to the intensity of the illumination in a particular area.
  • the charge pattern remaining after exposure is then developed, i.e., rendered visible, by treatment with a medium comprising electrostatically attractable particles having optical density.
  • the developing electrostatically attractable particles can be in the form of a dust, i.e., powder, a pigment in a resinous carrier, i.e., toner, or a liquid developer may be used in which the developing particles are carried in an electrically insulating liquid carrier.
  • a dust i.e., powder
  • a pigment in a resinous carrier i.e., toner
  • a liquid developer may be used in which the developing particles are carried in an electrically insulating liquid carrier.
  • EXAMPLE 1 0.056 gram of 4-anisyl-2,G-diphenylthiapyrylium perchlorate sensitizer was dissolved in 8 grams of solvent comprising equal weights of cyclohexanone and methyl alcohol. To this solution was then added with stirring 39 grams of 1,2-dichloropropane and 6 grams of triphenylamine photoconductor followed by 37 grams of 1,2-dichloropropane containing 30 percent of a polyester sold under the trade name of Vitel PE101X by the Goodyear Tire and Rubber Company. The solution was coated on thin aluminum foil with a 0.002 inch coating knife. The coating block was maintianed at 130 F. to promote rapid drying. Alternatively, this solution was coated onto transparent base coated with a transparent conducting layer, such as evaporated aluminum. I
  • the dried coating was given a negative corona discharge in a well-known manner and exposed for 8 seconds through a positive image transparency to a Kodak No. 1 Photoflood Lamp at a distance of 5 feet.
  • the resulting electrostatic latent image was rendered visibly by dusting with an electrostatically attractable powder having optical density according to the method described in US. Patent 2,297,691. A high quality positive image of the transparency was obtained.
  • the photoelectric speed values given in the following table are based on the following arbitrary speed scale.
  • the relative speed value of 20 was given to a coating when 57 foot candle seconds of illumination from a 3000" K. tungsten source reduced an electrostatic charge just to the point where no toner would be held by the coating on development.
  • a coating which required twice this amount of illumination or 114 foot candle seconds to discharge would have a relative speed of 10 and coatings requiring less than 57 foot candle seconds would have speed values greater than 20.
  • Example 2 The resulting element was then charged as in Example 1 and exposed from behind a 0.16 log E step tablet to a 300-watt tungsten exposure source at 9 inches for 30 seconds.
  • Table II Compounds of the example which would not require a binder were prepared and processed in the same manner except that the coating was prepared by dissolving 2 grams of the photoconductor in tetrahydrofuran to which the same amount of sensitizer was added. Coatings 14 and 15 were prepared in dichloromethane.
  • a method of preparation, for example, of 2,6-bis(4 ethylphenyl)-4-(4-n-amyloxyphenylthiapyrylium perchlorate comprises mixing 11 grams (0.02 mole) of 2,6-bis (4- ethylphenyl) -4- (4-n-amyloxyphenyl) pyrylium perchlorate in 400 ml. of acetone to which was added a solution of grams Na S.9I-I O in 100 ml. of water and allowing the preparation to stand at room temperature for onehalf hour after which a 100 ml. solution of percent perchloric acid diluted with 400 ml. of water was added with good stirring. After allowing to stand at room temperature for about two hours, the preparation was washed with ligroin to give a yield of 10 grams.
  • the pyrylium salt used in the above preparation was prepared by mixing 8.3 grams (0.018 mole) of the crude 1,5-bis(4-ethylphenyl) 3 (4-n-amyloxyphenyl)pentan- 1,5-dione with 10 ml. of boron fluoride ethyl ether and allowing the preparation to stand one hour at room temperature followed by warming for one hour on a steam bath. After cooling to room temperature, the preparation was dissolved in 75 ml. of ethyl alcohol containing 2 ml. of 70 percent perchloric acid. The preparation was then filtered, washed with ether and dried to give a yield of about 5.0 grams.
  • 2,4-diphenyl-6(3,4 diethoxystyryl)pyrylium perchlorate cited in a previous example can be prepared by condensing 2,4-diphenyl-6- methyl pyrylium perchlorate with 3,4-diethoxybenzaldehyde.
  • the sensiti zer compound of Example 1, 4 an isyl 2,6-' diphenylthiapyrylium perchlorate, was prepared by mixing 14 grams of anisaldehyde, 25 grams of acetophenone and 35 ml.' of phosphoryl chloride'and warming to 50 C. in a constant temperature bath for two hours. The excess phosphoryl chloride was removed by evaporation and the residue dissolved in 500 ml. of warm alcohol. Some insoluble material was removed by filtration and 10 ml. of perchloric acid (72 percent) was added to the filtrate. The mixture was allowed to stand two hours and the solid was collected, dried and recrystallized from acetonitrile to yield about 13 grams of product.
  • the product was then added to a solution of about 8 grams in about 320 ml. of acetone containing 8 grams of sodium sulfide dissolved in ml. of water.
  • the resulting solution was allowed to stand at room temperature for 0.5 hour and then 80 ml. of 20 percent perchloric acid diluted with 320 ml. of water was added. After standing for two hours, the final thiapyrylium product of the example was collected, dried and recrystallized from acetic anhydride.
  • a ph-otoconducti've composition consisting essentially of (a) an aryl amine selected from the group consisting of diaryl amines and triaryl amines and a sensitizing amount of (b) a member selected from the group consisting of pyrylium, thiapyrylium and selenapyrylium salts.
  • sensitizing compound is 2,6-diphenyl-4-(4-metl1- oxyphenyl) thiapyrylium fluoborate.
  • sensitizing compound is 2,6-bis(4-ethylphenyl)-4- (4-n-amyloxyphenyl)thiapyrylium perchlorate.
  • sensitizing compound is 2,6-bis(4-methoxypheny1)- 4-(4-n-amyloxyphenyl)thiapyrylium perchlorate.
  • sensitizing compound is 2,4,6-tri(4-methoxyphenyl) thiapyrylium perchlorate.
  • a photoconductive composition consisting essentially of (a) an aryl amine selected from the group consisting of diaryl amines and triaryl amines which are not also pyrylium, thiapyrylium, and selenapyrylium salts and a sensitizing amount of (b) a member selected from the group consisting of pyrylium, thiapyrylium, and selenapyrylium salts.
  • An electrophotographic element comprising a sheet of support material and coated thereon a photoconductive insulating layer comprising the photoconductive composition defined in claim 1.
  • An electrophotographic element comprising a sheet of support material andcoated thereon a photoconduc- 9 10 tive, electrically insulating layer consisting essentially of ductive composition as defined in claim 7 dispersed in any the photoconductive composition defined in claim 1 dis insulating resin binder. persed in an electrically insulating resin binder.
  • References Cited in the file of this Patent 12 An electrophotographic element comprising a sheet of support material and coated thereon a photoconduc- 5 UNITED STATES PATENTS tive electrically insulating layer comprising a photocon- 2,461,484 Thompson Feb. 8, 1949

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Description

United States Patent O 3,141,770 ELECTROPHOTOGRAPHIC LAYERS AND SENSITIZERS FOR SAME Dale R. Davis, Cornelia C. Natale, and Charles J. Fox,
Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Dec. 29, 1961, Ser. No. 163,017 12 Claims. (Cl. 96-1) The present invention relates to electrophotography and to photoconductive substances for preparing photoconductive layers for use in processes of electrophotography. More particularly, the present invention relates to such layers having incorporated novel sensitizing compounds.
Electrophotographic processes which depend on photoconductive layers include (a) xerographic processes in which, for example, a photoconductive layer on an electrically conducting support is provided with a uniform electrostatic charge in the dark, given an image exposure to light which causes the charge to be selectively dissipated in proportion to the intensity of the incident radiation, and then toned with a powder having optical density which adheres in the areas of residual charge, and (b) photoconductographic processes in which, for example, a photoconductive layer provides in areas of image exposure sufficient conductivity to enable formation of a visible image by an electrolytic process activated by an externally applied source of electric current. Processes of these types have been described in such US. and foreign patents as US. 2,297,691; 2,551,- 582 and in British 188,030 and 464,112.
Photoconductive layers for use in electrophotographic processes of the present type have been prepared in the past using such photoconductors as selenium, cadmium sulfide and zinc oxide. More recently, certain organic compounds have been proposed for use as photoconductors in photoconductive layers. Organic compounds, although preferred for other reasons, such as their capacity to form transparent layers and the like, have not shown in many cases a sensitivity to light to give the speed values desired in layers of this type. A number of sensitizing compounds have been disclosed recently in the prior art for use with certain of the organic-type photoconductor compounds. It is an object of the present invention to disclose still other classes of sensitizing compounds for use in combination with certain organic photoconducting compounds so that improved speed in photoconducting layers is obtained. An object of the present invention, accordingly, is to provide novel sensitizing compounds for use in photoconductive electrophotographic layers. Another object is to provide novel photoconductive layers having improved photoelectric speed. Other objects will become apparent from a reading of the specification and appended claims.
These objects are accomplished by incorporating in arylamine-incorporated photoconductive layers a sensitizing compound for said arylamine comprising a member selected from the group consisting of pyrylium salts and thiapyrylium salts. Arylamines to which we refer in the present specification comprises (1) diarylamines such as diphenylarnine, dinaphthylamine, N,N-diphenylbenzidine, N-phenyl-l-naphthylamine, N-phenyl-Z-naphthylamine, N,N-diphenyl-p-phenylenediamine, 2-carboxy-5-chloro- 4'-methoxydiphenylamine, p-anilinophenol, N,N'-di-2- naphthyl-p-phenylene diamine, and the like, and (2) triarylamines including (a) nonpolymeric triarylamines, such as triphenylamine, N,N,N,N-tetraphenylbenzidine, N,N,N,N-tetraphenyl-p phenylenediamine, N,N,N,N'- tetraphenyl-m-phenylenediamine, acetyltriphenylamine, hexanoyltriphenylarnine, lauroyltriphenylamine, hexyltriphenylamine, dodecyltriphenylamine, hexaphenylpararosaniline, 4,4-bis(diphenylamino)benzil, 4,4-bis(diphen- Arylamine compounds of the type described and meth ods for preparing them have been described in our two copending applications filed on even date herewith in the names of C. J. Fox et al. and C. J. Fox, respectively.
Pyrylium salts and thiapyrylium salts of the present invention comprise compounds represented by the following general formula:
wherein R R and R may each represent an aliphatic group having from 1 to 15 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, amyl, isoamyl, hexyl, octyl, nonyl, dodecyl, vinyl, styryl, alkoxystyryl, diethoxystyryl, dimethylaminostyryl, 1-butyl-4-pdimethylaminophenyl-1,3-butadienyl, ,B-ethyl-4-dimethylaminostyryl; an alkoxy group such as methoxy, ethoxy, propoxy, butoxy, amyloxy, hexoxy, octoxy, etc.; aryl, such as phenyl, 4-biphenyl, alkphenyl, such as 4-ethylphenyl, 4-propylphenyl, etc., alkoxyphenyl, e.g., 4-ethoxyphenyl,- 4-methoxyphenyl, 4-amyloxyphenyl, 2-hexoxyphenyl, Z-methoxyphenyl, 2-arnyloxyphenyl, 3,4-dimethoxyphenyl, etc.; w-hydroxy alkoxyphenyl, e.g., 2- hydroxyethoxyphenyl, 3-hydroxyethoxyphenyl, etc., 4- hydroxyphenyl, halophenyl, e.g., 3,4-dichlorophenyl, 3,4- dibromophenyl, 4-chlorophenyl, 2,4-dichlorophenyl, etc., azidophenyl, nitrophenyl, etc., aminophenyl, e.g., 4-diethylaminophenyl, 4-dimethylaminophenyl, etc.; X is a hetero atom, such as oxygen, sulfur and selenium; and Y is an anionic function.
Typical members of the present pyrylium and thiapyrylium salts include the following: 7
Compound Number Name of Compound 2,4,6-Triphenylpyryliutn perchlorate. 4-(4-Methoxyphenyl)-2,6-diphenylpyryliu m perchlorate 4-(2,1-Dichl0rophenyl)-2,6-diphenylpyrylium perchlora e. 4-(3,i-Dichlorophenyl)-2,6-diphenylpyrylium perchlora e. 2,6-Bis(4-rnethoxyphenyl)-4-phenylpyrylium perchlorate. fi-(-Methoxyphenyl)-2,4-diphenylpyrylium perchlorate. 2-(3,4-Dlchlor0phenyl)-4-(4-meth0xyphenyl)-6-phenylpyrylium perchlorate. 4-(4-Arnyloxyphenyl)-2,6-bis(4-cthylphenyl)pyrylium perchlorate. 4-(4-Amyloxypheny1)-2,6-bis(4-methoxyphenyl)pyrylium perchlorate. 2,4,6-Triphenylpyrylium fluoborate. 2,6-Bis(4-ethylphenyl)-4-(4-methoxyphenyl)pyrylium perchlorate. 2,6-Bis(4-ethylphenyl)-4-(4-rneth0xyphenyl)pyrylium fluobcrate. fi-(igl-Diethoxystyryl)-2,4-diphenylpyrylium perchlo- 6-(3,4-Diethoxy-fi-amy1styryl) -2,4-diphenylpyrylium flucborate.
6-(4-D imethylarnino-B-ethylstyryl) -2,4-diphenylpyrylium fluoborate. I
6-(l-n-Amylt-p-dimethylalni nopheny1-1,3-bntadienyl)- 2,4-diphenylpyry1ium fluoborate.
6-(4 Dirnethylarninostyryl)-2,4-diphenylpyrylium fluoborate.
6-(a-Ethyl-B,B-dimcthylaminophenyl vinylene)-2,4-
diphenylpyrylium fluoboratc.
6-(1-B utyl-4p-dimethylarninophenyl-l,3-butadienyl) 2,4-diphenylpyrylium fluoborate.
G-( t-Dimethylaruinostyryl)-2,4-diphenylpyrylium perchlorate.
fi-[flfi-Bis(4-dimethylamin0phcnyl)vinylene]-2,4-diphenylpyrylium perchlorate.
24 pyrylium tluoborate.
. 6-(1 Ethyli-p-dimethylaminophenyl-1,3-butadienyl)- z'A diphenylpyrylium fluoborate. 25 6-[fl,fl-Bis(4-dirnethylaminophenyl)vlnylene]-2,4-
diphenylpyrylium fluoborate. 26 6=(l Methyli-p-dimethylaminophenyl 1,3-butadienyl)- 2,4-diphenylpyryliurn fluoborate. 27 4-(4-Dimethylaminophenyl)-2,6-diphenylpyrylium perchlorate.
28; i 2,6 Bis(4-ethylphenyl)-4-phenylpyrylium perchlorate.
2,6-Bls( i-ethylphenyl)-4-n1ethoxyphenylthiapyrylium fluoborate.
2,4,G-triphenyltniapyrylium perchlorate.
4-(4.-Methoxyphenyl)-2,6-diphenylthiapyrylium perchlorate.
j 6-(4'-Methoxyphenyl)-2,4-diphenylthiapyrylium perchlorate. 4
2,6-Bis(4-rnethoxyphenyl) -4-phenylth1apyryl1um perchlorate.
4-(2,4-Dichlorophenyl)-2,6-diphenylthiapyrylium perchlorate.
2,4,G-Trl( t-methoxyphenyl)thiapyrylium perchlorate.
2,6-Bis(4ethylphenyl)-4-phenylthiapyrylium perchlorate 4-(4-An1yloxypheny1)-2,6-b1s(4-ethylphenyl)thiapyryliurn perchlorate. 6-(4-Dimethylaminostyryl)-2,4-diphcnylthiapyryliur perchlorate. 2,4,6-Triphenylthiapyrylium fluoborate. 2,4,6-Triphenylthiapyrylium sulfate.
4-(4-Methoxyphenyl)-2,6-diphenylth1apyryhum fluoborate. 2,4,6-Triphenylthiapyrylium chloride. 2-(4-Amyloxyphenyl)-4,6-diphenylthiapyrylium fluoborate.
44; 4-(4-Amyloxyphenyl)-2,6-bis(4-rnethoxyphenyl)thiapyryllum perchlorate. 45 2,6-Bis(4ethylphenyl)4-(4-methoxyphenyl)thiapyryl- I ium perchlorate. 46 4-Afiiisyl- 2,6'-bis(4-n-amyloxyphenyl)thiapyryhum c lor' e. 47 2-[fl,B-Bis( t-dimethylaminophenyl)vinylene]4,6-
' diphenylthiapyryliurn perchlorate. 48 fi-(fl-Ethyl-4-dimethylaminostyryl)-2,4-d1phenylth1apyrylium perchlorate. 2-(3,4eDiethoxystyryl) -4,6-diphenylth1apyryl1um perchlorate. 2,4,6-Trianisylthiapyrylium perchlorate.
G-Ethyl-zA-diphenylpyryliumfluoborate. 2,6-Bis(4-ethylphenyl)4-(4-methoxyphenyl)thlapyrylium chloride. 53 6-[fi,B-Bi's(4-dimethylaminophenyl)v1nylene]-2,4-d1(4- ethylphenybpyrylium perchlorate. v 2,6-Bis(4-amyloxyphenyl)-4-(4-methoxyphenyl)thiapyrylium perchlorate.
55 6-(BA-Diethoxy-B-ethylstyryl)-2,4-diphenylpyryliurn fluoborate.
56 6-(4-Methoxy-B-ethylstyryl)-2,4-d1phenylpyryhun1 fluoborate.
57; 2'-(4'ethylphenyl)-4,6diphenylthiapyryhu.rn perchlorate.
58 2,6-diphenyl-4-(4-methoxyphenyl)thlapyryhum perchlorate. A
59 2,6-diphcnyl-4-(4-methoxyphenyl)thiapyrylium fiuoborate.
60 2,6-bis(4ethylphenyl)-4-(4-n-amyloxyphenyD- thiapyryliurn perchlorate. V
61 2,6 bis(4'-ruethoxyphenyl)-4-(4-n-arnyloxyphenyl)- thiapyrylium perchlorate.
62 v 2,4,6-tri(4-rnethoxyphenyl)thiapyryhun fiuoborate.
63 2,4-diphenyl-6(3,4-diethoxystyryl)pyrylium perchlorate.
In preparing photoconductive layers of the present invention, it is the usual practice to dissolve the photoconductive substance in a suitable solvent in the presence of an electrically insulating binder and then to dissolve particular composition to give optimum sensitization can vary widely. The optimum amount will, of course, vary with the arylamine photoconductor employed as wellas with the particular sensitizing compound. In general, substantial speed gains can be obtained where an appropriate sensitizer is added at a concentration in a range from about 0.0001 to 30 percent by weight based on the weight of the film-forming hydrophobic composition.
The amount of sensitizer which can be addedgtoda acrylonitrile copolymers; poly(vinyl acetate); vinyl acetate, vinyl chloride copolymers; poly(vinyl acetals), such as poly(vinyl butyral); polyacrylic and methacrylic esters, such as poly(methyl methacrylate), poly(n-butyl methacrylate), poly(isobutyl) methacrylate), etc.; polystyrene; nitrated polystyrene; polymethylstyrene; isobutylene polymers; polyesters, such as poly(ethylene alkaryloxyalkylene terephthalate); phenol-formaldehyde resins; ketone resins; polyamide; polycarbonates; etc. Methods of making resins of this type have been described in the prior art, for example, styrene-alkyd resins can be prepared according to the method described in US. Patents 2,361,019 and 2,258,423. Suitable resins of the type contemplated for use in the photoconductive layers of this invention are sold under such trade names as Vitel PE-lOl-X, Cymac, Piccopale 100, and Saran F- 220. Other types of binders which can be used in the photoconductive layers of the invention include such materials as paraflin, mineral Waxes, etc.
Solvents of choice for preparing coating compositions of the present invention can include a number of solvents such as benzene, toluene, acetone, Z-butanone, chlorinated hydrocarbons, e.g., methylene chloride, ethylene chloride, etc. ethers, e.g., tetrahydrofuran, or mixtures of these solvents, etc.
Photoconductive layers of the present invention can be coated on a conducting support in any well-known manner such as doctor-blade coating, swirling, dip-coat ing, and the like. Photoconductive layers of the invention in some cases do not require a binder, for example, where certain polymeric arylamines are employed. However, it has been found beneficial sometimes to include in a coating composition of this type at least some binder, for example,. as little as 1 weight percent.
In preparing the coating composition, useful results were obtained where the photoconductor substance was present in an amount equal to at least about 1 weight percent of the coating composition. The upper limit in the amount of photoconductor substance present is not critical. As indicated previously, the polymeric materials of thepresent invention in many cases do not require a binder in order to obtain a self-supporting coating on the support. In those cases Where a binder is employed, it.
is normally required that the photoconductor substance be present in an amount from about 1 weight percent of the coating composition to about 99 weight percent of the coating composition. A preferred weight range for the photoconductor substance in the coating composition is from 10 weight percent to about 60 weight percent.
Coating thicknesses of the photoconductive composition on a support can vary widely. Normally a wet coating in the range from about 0.001 inch to about 0.01 inch was useful for the invention. The preferred range of Wet coating thickness was found to be in the range from about 0.002 inch to about 0.006 inch.
Suitable supporting materials for coating the photoconductive layers of the present invention can include any of the electrically conducting supports, for example, paper (at a relative humidity above 20 percent); aluminum-paper laminates; metal foils, such as aluminum foil, zinc foil, etc.; metal plates, such as aluminum, copper, zinc, brass, and galvanized plates; regenerated cellulose and cellulose derivatives; certain polyesters, especia1- ly polyesters having a thin electroconductive layer (e.g., cuprous iodide) coated thereon; etc. ing materials can also include the humidity-independent conducting layers of semiconductors dispersed in, poly:
Suitable support'-.
meric binders, as described in US. application Serial No. 56,648, filed September 19, 1960.
The elements of the present invention can be employed in any of the well-known electrophotographic processes which require photoconductive layers. One such process is the xerographic proces. In a process of this type, the electrophotographic element is given a blanket electrostatic charge by placing the same under a corona discharge which serves to give a uniform charge to the surface of the photoconductive layer. This charge is retained by the layer owing to the substantial insulating property of the layer, i.e., the low conductivity of the layer in the dark. The electrostatic charge formed on the surface of the photoconducting layer is then selectively dissipated from the surface of the layer by exposure to light through a negative by a conventional exposure operation such as, for example, by contact-printing technique, or by lens projection of an image, etc., to form a latent image in the photoconducting layer. By exposure of the surface in this manner, a charged pattern is created by virtue of the fact that light causes the charge to leak away in proportion to the intensity of the illumination in a particular area. The charge pattern remaining after exposure is then developed, i.e., rendered visible, by treatment with a medium comprising electrostatically attractable particles having optical density. The developing electrostatically attractable particles can be in the form of a dust, i.e., powder, a pigment in a resinous carrier, i.e., toner, or a liquid developer may be used in which the developing particles are carried in an electrically insulating liquid carrier. Methods of development of this type are widely known and have been described in the patent literature in such patents, for example, as US. Patent 2,296,691 and in Australian Patent 212,315. In processes of electrophotographic reproduction such as in xerography, by selecting a developing particle which has as one of its components, a low-melting resin, it is possible to treat the developed photoconductive material with heat and cause the powder to adhere permanently to the surface of the photoconductive layer. In other cases, a transfer of the image formed on the photoconductive layer can be made to a second support which would then become the final print. Techniques of the type indicated are well known in the art and have been described in a number of Us. and foreign patents, such as US. Patent 2,297,691 and 2,551,582 and in RCA Review, vol. (1954), pages 469-484.
The invention will now be further described by reference to the following examples.
EXAMPLE 1 0.056 gram of 4-anisyl-2,G-diphenylthiapyrylium perchlorate sensitizer was dissolved in 8 grams of solvent comprising equal weights of cyclohexanone and methyl alcohol. To this solution was then added with stirring 39 grams of 1,2-dichloropropane and 6 grams of triphenylamine photoconductor followed by 37 grams of 1,2-dichloropropane containing 30 percent of a polyester sold under the trade name of Vitel PE101X by the Goodyear Tire and Rubber Company. The solution was coated on thin aluminum foil with a 0.002 inch coating knife. The coating block was maintianed at 130 F. to promote rapid drying. Alternatively, this solution was coated onto transparent base coated with a transparent conducting layer, such as evaporated aluminum. I
In either case, the dried coating was given a negative corona discharge in a well-known manner and exposed for 8 seconds through a positive image transparency to a Kodak No. 1 Photoflood Lamp at a distance of 5 feet. The resulting electrostatic latent image was rendered visibly by dusting with an electrostatically attractable powder having optical density according to the method described in US. Patent 2,297,691. A high quality positive image of the transparency was obtained.
6 EXAMPLE 2 EXAMPLE 3 This example shows the improved speed obtained using various sensitizers in electrophotographic materials of the invention where triphenylamine is employed at a 30 percent by weight concentration as the photoconductor sub stance in a 70 percent polyester photoconductive layer. The polyester is a copolymer obtained from terephthalic acid and a glycol mixture of 2,2-bis [4-(B-hydroxyethoxy) phenyl] propane and ethylene glycol (9:1).
The photoelectric speed values given in the following table are based on the following arbitrary speed scale. The relative speed value of 20 was given to a coating when 57 foot candle seconds of illumination from a 3000" K. tungsten source reduced an electrostatic charge just to the point where no toner would be held by the coating on development. Thus, a coating which required twice this amount of illumination or 114 foot candle seconds to discharge would have a relative speed of 10 and coatings requiring less than 57 foot candle seconds would have speed values greater than 20.
Table I sensitizer Concentra- Arylamine tion in Photoconduetor sensitizer Moles/100 Speed Moles of Nitrogen inLayer- Triphenylamine None None .01 Do 2,4,G-Triphenyl-thlapyryl- 0.5 8
ium fluoborate. D0 2'(4ethylphenyl)-4,6- 0.5 15
diphenyl thiapyryllum perchlorate. Do 2,6-diphenyl-4-(4-methoxy- 0.5 20 phenyD-thiaphyrylium l 0 60 perchlorate. 2. 0 Do 2,6-diphenyl-4-(4-methoxy- 0.5 12
phenyD-thiapyrylium fluobor 0. Do 2,6-bis(4-ethylphenyl)4-(4- 0.1 8 n-amyl0xyphenyl)- 0. 2 12 thiapyrylinm perchlorate. 0.3 30 0.4 40 0.5 60 Do 2,6-bis(4-methoxyphenyl)- 0.5 6
4-phenyl-thiapyrylium chloride. Do 2,6-bis(4-meth0xyphenyl)- 0.5 60
4-(4-n-amyloxyphenyD- thiapyryllum perchlorate. Do 2,4,6-tris(4-methoxyphenyl)- 0.5 50 thiapyrylium perchlorate. 1.0 80 2.0 Do 2,4-diphenyl-6(3,4- 0.5 10
diethoxystyryl) pyrylium perchlorate. 1
1 Polystyrene replaced Vitel PE-lOl-X as binder.
EXAMPLE 4 Coatings of triphenylamine derivatives were prepared and sensitized as follows:
In coatings of the example containing a binder, 0.5 gram of the particular photoconductor compound was dissolved in a solution of 2 grams of either polystyrene or Vitel PE-lOl-X in 15 ml. of tetrahydrofuran. To the resulting dope was added 0.025 g. of 2,6-bis(4-ethylphenyl)-4-(4-amyloxyphenyl)thiapyrylium perchlorate in 0.5 ml. of tetrahydrofuran. This dope was then coated on a conducting support and dried... The resulting element was then charged as in Example 1 and exposed from behind a 0.16 log E step tablet to a 300-watt tungsten exposure source at 9 inches for 30 seconds. The results are shown in Table II. Compounds of the example which would not require a binder were prepared and processed in the same manner except that the coating was prepared by dissolving 2 grams of the photoconductor in tetrahydrofuran to which the same amount of sensitizer was added. Coatings 14 and 15 were prepared in dichloromethane.
Table II Visible steps Image obtained Derivative Poly- Vitel styrene 1 N binder.
Substantially no image was obtained at the exposure level used in the example in control coatings where the coatings were prepared in the same manner as those of Table II except without the use of a thiapyrylium salt sensitizing compound.
Methods for preparing pyrylium and thiapyrylium salts.
suitable for use in the present invention has been described in the prior art, for example, in Helvetica ChimicaActa, 39, 214-216 (1956). V
A method of preparation, for example, of 2,6-bis(4 ethylphenyl)-4-(4-n-amyloxyphenylthiapyrylium perchlorate comprises mixing 11 grams (0.02 mole) of 2,6-bis (4- ethylphenyl) -4- (4-n-amyloxyphenyl) pyrylium perchlorate in 400 ml. of acetone to which was added a solution of grams Na S.9I-I O in 100 ml. of water and allowing the preparation to stand at room temperature for onehalf hour after which a 100 ml. solution of percent perchloric acid diluted with 400 ml. of water was added with good stirring. After allowing to stand at room temperature for about two hours, the preparation was washed with ligroin to give a yield of 10 grams. I V
The pyrylium salt used in the above preparation was prepared by mixing 8.3 grams (0.018 mole) of the crude 1,5-bis(4-ethylphenyl) 3 (4-n-amyloxyphenyl)pentan- 1,5-dione with 10 ml. of boron fluoride ethyl ether and allowing the preparation to stand one hour at room temperature followed by warming for one hour on a steam bath. After cooling to room temperature, the preparation was dissolved in 75 ml. of ethyl alcohol containing 2 ml. of 70 percent perchloric acid. The preparation was then filtered, washed with ether and dried to give a yield of about 5.0 grams.
In another method of preparation, 2,4-diphenyl-6(3,4 diethoxystyryl)pyrylium perchlorate cited in a previous example can be prepared by condensing 2,4-diphenyl-6- methyl pyrylium perchlorate with 3,4-diethoxybenzaldehyde.
The sensiti zer compound of Example 1, 4 an isyl 2,6-' diphenylthiapyrylium perchlorate, was prepared by mixing 14 grams of anisaldehyde, 25 grams of acetophenone and 35 ml.' of phosphoryl chloride'and warming to 50 C. in a constant temperature bath for two hours. The excess phosphoryl chloride was removed by evaporation and the residue dissolved in 500 ml. of warm alcohol. Some insoluble material was removed by filtration and 10 ml. of perchloric acid (72 percent) was added to the filtrate. The mixture was allowed to stand two hours and the solid was collected, dried and recrystallized from acetonitrile to yield about 13 grams of product. The product was then added to a solution of about 8 grams in about 320 ml. of acetone containing 8 grams of sodium sulfide dissolved in ml. of water. The resulting solution was allowed to stand at room temperature for 0.5 hour and then 80 ml. of 20 percent perchloric acid diluted with 320 ml. of water was added. After standing for two hours, the final thiapyrylium product of the example was collected, dried and recrystallized from acetic anhydride.
Many pyrylium and thiapyrylium salts suitable for use in the present invention and methods of preparation have been described in our copending application VanAllan et al., entitled Light-Sensitive Layers Containing Pyrylium and Thiapyrylium Salts, Serial No. 146,743, filed October 23, 1961.
The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A ph-otoconducti've composition consisting essentially of (a) an aryl amine selected from the group consisting of diaryl amines and triaryl amines and a sensitizing amount of (b) a member selected from the group consisting of pyrylium, thiapyrylium and selenapyrylium salts.
2. The photoconductive composition of claim 1 wherein said sensitizing compound is 2,6-diphenyl-4-(4-methoxyphenyl)thiapyrylium perchlorate.
3. The photocon'ductive composition of claim 1 wherein said sensitizing compound is 2,6-diphenyl-4-(4-metl1- oxyphenyl) thiapyrylium fluoborate.
4. The photoconductive composition of claim -1 wherein said sensitizing compound is 2,6-bis(4-ethylphenyl)-4- (4-n-amyloxyphenyl)thiapyrylium perchlorate.
5. The photoconductive composition of claim 1 wherein said sensitizing compound is 2,6-bis(4-methoxypheny1)- 4-(4-n-amyloxyphenyl)thiapyrylium perchlorate.
6. The photoconductive composition of claim 1 wherein said sensitizing compound is 2,4,6-tri(4-methoxyphenyl) thiapyrylium perchlorate.
7. A photoconductive composition consisting essentially of (a) an aryl amine selected from the group consisting of diaryl amines and triaryl amines which are not also pyrylium, thiapyrylium, and selenapyrylium salts and a sensitizing amount of (b) a member selected from the group consisting of pyrylium, thiapyrylium, and selenapyrylium salts.
8. The photoconductive composition of claim 1 wherein said aryl amine is triphenyl amine.
9. The photoconductive composition of claim 1 where in'said sensitizing amount of component (b) is in the range of from about 0.1 to about 2 mols per mols of nitrogen present in component (a),
10. An electrophotographic element comprising a sheet of support material and coated thereon a photoconductive insulating layer comprising the photoconductive composition defined in claim 1.
11. An electrophotographic element comprising a sheet of support material andcoated thereon a photoconduc- 9 10 tive, electrically insulating layer consisting essentially of ductive composition as defined in claim 7 dispersed in any the photoconductive composition defined in claim 1 dis insulating resin binder. persed in an electrically insulating resin binder. References Cited in the file of this Patent 12. An electrophotographic element comprising a sheet of support material and coated thereon a photoconduc- 5 UNITED STATES PATENTS tive electrically insulating layer comprising a photocon- 2,461,484 Thompson Feb. 8, 1949

Claims (1)

1. A PHOTOCONDUCTIVE COMPOSITION CONSISTING ESSENTIALLY OF (A) AN ARYL AMINE SELECTED FROM THE GROUP CONSISTING OF DIARYL AMINES AND TRIARYL AMINES AND A SENSITIZING AMOUNT OF (B) A MEMBER SELECTED FROM THE GROUP CONSISTING OF PYRYLIUM, THIAPYRYLIUM AND SELENAPYRYLIUM SALTS.
US163017A 1961-10-23 1961-12-29 Electrophotographic layers and sensitizers for same Expired - Lifetime US3141770A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
DENDAT1252060D DE1252060B (en) 1961-10-23
BE626528D BE626528A (en) 1961-10-23
BE623972D BE623972A (en) 1961-10-23
US146743A US3250615A (en) 1961-10-23 1961-10-23 Light-sensitive layers containing pyrylium and thiapyrylium salts
US163017A US3141770A (en) 1961-10-23 1961-12-29 Electrophotographic layers and sensitizers for same
DE19621572340 DE1572340B1 (en) 1961-10-23 1962-10-11 Photoconductive layer
FR913039A FR1359095A (en) 1961-10-23 1962-10-22 New photosensitive layers
GB40183/62A GB1023377A (en) 1961-10-23 1962-10-23 Improvements in or relating to light-sensitive layers
JP5285962A JPS3911543B1 (en) 1961-12-29 1962-11-24
DEP1269A DE1269488B (en) 1961-10-23 1962-12-12 Sensitized photoconductive layer
FR919425A FR86809E (en) 1961-10-23 1962-12-21 New photosensitive layers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US146743A US3250615A (en) 1961-10-23 1961-10-23 Light-sensitive layers containing pyrylium and thiapyrylium salts
US163017A US3141770A (en) 1961-10-23 1961-12-29 Electrophotographic layers and sensitizers for same

Publications (1)

Publication Number Publication Date
US3141770A true US3141770A (en) 1964-07-21

Family

ID=26844255

Family Applications (2)

Application Number Title Priority Date Filing Date
US146743A Expired - Lifetime US3250615A (en) 1961-10-23 1961-10-23 Light-sensitive layers containing pyrylium and thiapyrylium salts
US163017A Expired - Lifetime US3141770A (en) 1961-10-23 1961-12-29 Electrophotographic layers and sensitizers for same

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US146743A Expired - Lifetime US3250615A (en) 1961-10-23 1961-10-23 Light-sensitive layers containing pyrylium and thiapyrylium salts

Country Status (5)

Country Link
US (2) US3250615A (en)
BE (2) BE626528A (en)
DE (3) DE1572340B1 (en)
FR (2) FR1359095A (en)
GB (1) GB1023377A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485625A (en) * 1966-06-09 1969-12-23 Eastman Kodak Co Photoconductive elements containing 2,3,4,5-tetraaryl pyrrole
US3503740A (en) * 1967-07-18 1970-03-31 Eastman Kodak Co Photoconductive elements containing organic photoconductors and sensitizers
US3525612A (en) * 1965-06-16 1970-08-25 Eastman Kodak Co Electrophotographic reproduction process employing a light sensitive material and a photoconductive material
US3607257A (en) * 1968-08-27 1971-09-21 Eastman Kodak Co Photoconductive compositions and elements
US3658520A (en) * 1968-02-20 1972-04-25 Eastman Kodak Co Photoconductive elements containing as photoconductors triarylamines substituted by active hydrogen-containing groups
US3658521A (en) * 1969-10-03 1972-04-25 Eastman Kodak Co 1-aminopyridinium dyes as sensitizers in electrophotographic layers
US3994724A (en) * 1969-07-23 1976-11-30 Scott Paper Company Photoconductor elements containing substituted aniline photoconductor compounds
US4167412A (en) * 1976-08-02 1979-09-11 Eastman Kodak Company Pyrylium sensitizers for photoconductive compositions
US4248952A (en) * 1978-02-14 1981-02-03 James River Graphics Inc. Technique for making electrical ground contact with the intermediate conductive layer of an electrostatographic recording member
US4555396A (en) * 1982-12-22 1985-11-26 Eastman Kodak Company Use of pyrylium and thiapyrylium compounds as biological stains
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US4840784A (en) * 1982-12-22 1989-06-20 Eastman Kodak Company Use of pyrylium and thiapyrylium compounds as biological stains
US5024911A (en) * 1987-06-03 1991-06-18 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor having an electric charge generating layer comprising a pyrylium compound

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1051201A (en) * 1963-02-26
US3434973A (en) * 1966-06-30 1969-03-25 Fmc Corp Pyrylium salts as pickling inhibitors
US3526502A (en) * 1966-07-18 1970-09-01 Matsushita Electric Ind Co Ltd Electrophotographic material
US3549361A (en) * 1966-08-01 1970-12-22 Eastman Kodak Co Electrophotographic compositions and elements
US3533785A (en) * 1967-03-20 1970-10-13 Eastman Kodak Co Photoconductive compositions and elements
US3647429A (en) * 1967-07-03 1972-03-07 Eastman Kodak Co Photoconductive compositions and electrophotographic elements containing group iva or group va organometallic photoconductors
US3527602A (en) * 1967-08-31 1970-09-08 Eastman Kodak Co Organic photoconductors
DE1772688A1 (en) * 1968-06-20 1971-05-27 Agfa Gevaert Ag Sensitized photoconductive layers
US3652269A (en) * 1968-08-27 1972-03-28 Eastman Kodak Co Photoconductive elements containing halogenated polyethylene binders
US3653899A (en) * 1968-11-12 1972-04-04 Eastman Kodak Co Photographic materials and processes
JPS4825658B1 (en) * 1969-01-30 1973-07-31
US3647446A (en) * 1970-03-05 1972-03-07 Eastman Kodak Co Process for preparing high-relief printing plates
US3887366A (en) * 1971-03-30 1975-06-03 Ibm Cyanine pigments in electrophotographic processes
US3772028A (en) * 1972-02-02 1973-11-13 Eastman Kodak Co Sensitized photosensitive compounds and elements
US3938994A (en) * 1972-03-17 1976-02-17 Eastman Kodak Company Pyrylium dyes for electrophotographic composition and element
US3973962A (en) * 1974-05-02 1976-08-10 Eastman Kodak Company Aggregate photoconductive composition containing combination of pyrylium dye salts
US4105447A (en) * 1975-07-14 1978-08-08 Eastman Kodak Company Photoconductive insulating compositions including polyaryl hydrocarbon photoconductors
JPS52126220A (en) * 1976-04-14 1977-10-22 Kimoto Kk Dry image forming material and method of forming image
US4173473A (en) * 1977-07-06 1979-11-06 Eastman Kodak Company Radiation sensitive compositions containing pyrylium compounds
CA1086410A (en) * 1977-08-02 1980-09-23 Ching W. Tang Organic photovoltaic elements
JPS5427387A (en) * 1977-08-02 1979-03-01 Eastman Kodak Co Optical electromotive force element
FR2409264A1 (en) * 1977-11-18 1979-06-15 Rhone Poulenc Ind PROCESS FOR PREPARING PYRYLIUM SALTS
US4283475A (en) * 1979-08-21 1981-08-11 Fuji Photo Film Co., Ltd. Pentamethine thiopyrylium salts, process for production thereof, and photoconductive compositions containing said salts
WO1983002612A1 (en) * 1980-02-28 1983-08-04 Katritzky, Alan, R. Thiopyrylium sensitizing dyes
US4384034A (en) * 1981-02-27 1983-05-17 Minnesota Mining And Manufacturing Company Thiopyrylium dye sensitized photoconductive materials
JPS5945303A (en) * 1982-09-07 1984-03-14 Nippon Oil & Fats Co Ltd Photo-initiator composition having high sensitivity
US4774250A (en) * 1987-04-02 1988-09-27 Dana Farber Cancer Institute Composition and method for treating differentiated carcinoma or melanoma cells with thiapyrylium dyes
US5468583A (en) * 1994-12-28 1995-11-21 Eastman Kodak Company Cyclic bis-dicarboximide electron transport compounds for electrophotography
US7449268B2 (en) * 2005-05-27 2008-11-11 Xerox Corporation Polymers of napthalene tetracarboxylic diimide dimers
US7390601B2 (en) * 2005-06-16 2008-06-24 Xerox Corporation Imaging member comprising modified binder
WO2017112668A1 (en) 2015-12-21 2017-06-29 University Of Maryland, Baltimore Small molecule lipid ii inhibitors
US10941114B2 (en) 2015-12-21 2021-03-09 University Of Maryland, Baltimore Small molecule lipid II inhibitors
EP3749657A4 (en) * 2018-02-06 2021-08-25 Council of Scientific & Industrial Research A process for the preparation of pyrylium salts

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461484A (en) * 1945-04-17 1949-02-08 Gen Aniline & Film Corp Pyrylium dye salts as filter and antihalation dyes in photographic materials

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US461484A (en) * 1891-10-20 Hot-air radiator
NL87862C (en) * 1951-08-20
US2811510A (en) * 1955-09-15 1957-10-29 Eastman Kodak Co Light-sensitive polymeric stilbazoles and quaternary salts thereof
US2956878A (en) * 1956-11-13 1960-10-18 Eastman Kodak Co Photosensitive polymers and their applications in photography
BE562336A (en) * 1956-11-14
NL250327A (en) * 1959-04-08

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2461484A (en) * 1945-04-17 1949-02-08 Gen Aniline & Film Corp Pyrylium dye salts as filter and antihalation dyes in photographic materials

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525612A (en) * 1965-06-16 1970-08-25 Eastman Kodak Co Electrophotographic reproduction process employing a light sensitive material and a photoconductive material
US3485625A (en) * 1966-06-09 1969-12-23 Eastman Kodak Co Photoconductive elements containing 2,3,4,5-tetraaryl pyrrole
US3503740A (en) * 1967-07-18 1970-03-31 Eastman Kodak Co Photoconductive elements containing organic photoconductors and sensitizers
US3533786A (en) * 1967-07-18 1970-10-13 Eastman Kodak Co Photoconductive elements containing ionic cycloheptenyl photoconductive compounds
US3658520A (en) * 1968-02-20 1972-04-25 Eastman Kodak Co Photoconductive elements containing as photoconductors triarylamines substituted by active hydrogen-containing groups
US3607257A (en) * 1968-08-27 1971-09-21 Eastman Kodak Co Photoconductive compositions and elements
US3994724A (en) * 1969-07-23 1976-11-30 Scott Paper Company Photoconductor elements containing substituted aniline photoconductor compounds
US3658521A (en) * 1969-10-03 1972-04-25 Eastman Kodak Co 1-aminopyridinium dyes as sensitizers in electrophotographic layers
US4167412A (en) * 1976-08-02 1979-09-11 Eastman Kodak Company Pyrylium sensitizers for photoconductive compositions
US4248952A (en) * 1978-02-14 1981-02-03 James River Graphics Inc. Technique for making electrical ground contact with the intermediate conductive layer of an electrostatographic recording member
US4555396A (en) * 1982-12-22 1985-11-26 Eastman Kodak Company Use of pyrylium and thiapyrylium compounds as biological stains
US4840784A (en) * 1982-12-22 1989-06-20 Eastman Kodak Company Use of pyrylium and thiapyrylium compounds as biological stains
US4661429A (en) * 1986-04-28 1987-04-28 Eastman Kodak Company Photoelectrographic elements and imaging method
US5024911A (en) * 1987-06-03 1991-06-18 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor having an electric charge generating layer comprising a pyrylium compound

Also Published As

Publication number Publication date
DE1252060B (en)
GB1023377A (en) 1966-03-23
FR1359095A (en) 1964-04-24
FR86809E (en) 1966-04-22
DE1572340B1 (en) 1970-04-23
BE623972A (en)
BE626528A (en)
US3250615A (en) 1966-05-10
DE1269488B (en) 1968-05-30

Similar Documents

Publication Publication Date Title
US3141770A (en) Electrophotographic layers and sensitizers for same
US3265496A (en) Photoconductive substances for electrophotography
US3820989A (en) Tri-substituted methanes as organic photoconductors
US3526501A (en) 4-diarylamino-substituted chalcone containing photoconductive compositions for use in electrophotography
US3567450A (en) Photoconductive elements containing substituted triarylamine photoconductors
US3542544A (en) Photoconductive elements containing organic photoconductors of the triarylalkane and tetraarylmethane types
US3658520A (en) Photoconductive elements containing as photoconductors triarylamines substituted by active hydrogen-containing groups
US3488705A (en) Thermally unstable organic acid salts of triarylmethane dyes as sensitizers for organic photoconductors
JPS5857739B2 (en) Hikaridendousei Seibutsu
US3234280A (en) Triphenylamine compounds and preparation thereof
US3677752A (en) Bis(dialkylaminoaryl)ethylene photoconductors
US3647433A (en) Dinitroarylmethine dyes as sensitizers in electrophotographic layers
US3655378A (en) Charge-transfer complexes of dibenzofuran-formaldehyde or dibenzothiophene-formaldehyde resins as photoconductive materials
US3938994A (en) Pyrylium dyes for electrophotographic composition and element
US3765884A (en) 1-substituted-2-indoline hydrazone photoconductors
US3533783A (en) Light adapted photoconductive elements
GB1560496A (en) Photoconductive compositions
US3705913A (en) Electrophotographic sensitizers
US3647432A (en) Carbazolylmethane dye salts as sensitizers for photoconductor compositions
US3719486A (en) Photoconductive elements containing organo-metallic photoconductors
US3586500A (en) Electrophotographic composition and element
US3652269A (en) Photoconductive elements containing halogenated polyethylene binders
US3591374A (en) Pyrylium dye overcoating of pyrylium dye sensitized photoconductive elements
US3533787A (en) Photoconductive elements containing polymeric binders of nuclear substituted vinyl haloarylates
US3784376A (en) Photoconductive element containing furans, indoles, or thiophenes